Summary
The novel theoretical scheme IMOMM, integrating ab initio and molecular mechanics contributions in a single geometry optimization process, is applied to the structural determination of different [OsO4(NR3)] (NR3 = bulky chiral alkaloid derivative) species closely related to active catalysts for the asymmetric dihydroxylation of olefins. Computed values compare in a satisfactory way with available X-ray data, the relationship between the Os-N distance and the nature of the NR3, ligand being properly reproduced. The computational scheme allows the separate quantification of electronic and steric effects, as well as the identification of the specific steric repulsions responsible for the difference.
This is a preview of subscription content, log in via an institution to check access.
Similar content being viewed by others
References
Kolb HC, VanNieuwenhze MS, Sharpless KB (1994) Chem Rev 94: 2483–2547, and references therein
Corey EJ, Noe MC (1993) J Am Chem Soc 115: 2579–2580
Kolb HC, Andersson PF, Bennani YL, Crispino GA, Jeong K-S, Kwong HL, Sharpless KB (1993) J Am Chem Soc 115: 12226–12227
Norrby P-O, Kolb HC, Sharpless KB (1994) Organometallics 13: 344–347
Veldkamp A, Frenking G (1994) J Am Chem Soc 116: 4937–4946
Norrby P-O, Kolb HC, Sharpless KB (1994) J Am Chem Soc 116: 8470–8478
Wu Y-D, Wang Y, Houk KN (1992) J Org Chem 57: 1362–1369
Maseras F, Morokuma K (1995) J Comp Chem 9: 1170–1179
Matsubara T, Maseras F, Koga N, Morokuma K (1996) J Phys Chem 100: 2573–2580
Griffith WP, Skapski AC, Woode KA, Wright MJ (1978) Inorg Chim Acta 31: L413-L414
Svendsen JS, Markò I, Jacobsen EN, Rao CP, Bott S, Sharpless KB (1989) J Org Chem 54: 2264–2266
Frisch MJ, Trucks GW, Schlegel HB, Gill PMW, Johnson BG, Wong MW, Foresman JB, Robb MA, Head-Gordon M, Replogle ES, Gomperts R, Andres JL, Raghavachari K, Binkley JS, Gonzalez C, Martin RL, Fox DJ, Defrees DJ, Baker J, Stewart JJP, Pople JA (1993) Gaussian 92/DFT, Gaussian Inc, Pittsburgh PA
Allinger NL (1992) mm3(92), QCPE, Bloomington, IN
Møller C, Plesset MS (1934) Phys Rev 46: 618
Becke AD (1988) Phys Rev A 38: 3098–3100 (b) Becke AD (1993) J Chem Phys 98: 5648–5652 (c) Lee C, Yang W, Parr RG (1988) Phys Rev B 37:785–789
Hay PJ, Wadt WR (1985) J Chem Phys 82: 299–310
Binkley JS, Pople JA, Hehre WJ (1980) J Am Chem Soc 102: 939–947
Hehre WJ, Ditchfield R, Pople JA (1972) J Chem Phys 56: 2257–2261 (b) Hariharan PC, Pople JA (1973) Theor Chim Acta 28:213
Apart from the modifications required by the method [8], all torsional contributions associated to dihedral angles involving the metal atom were set to zero. Finally, the very few parameters of complex 2 that are not provided by the program were set to values corresponding to similar atoms
In the ab initio calculation, the N-H distances were frozen to 1.015 Å. In the molecular mechanics calculation, the corresponding N-C distances were frozen to their experimental value in the X-ray structure of 2
Author information
Authors and Affiliations
Rights and permissions
About this article
Cite this article
Ujaque, G., Maseras, F. & Lledós, A. A theoretical evaluation of steric and electronic effects on the structure of [OSO4 (NR3)] (NR3 = bulky chiral alkaloid derivative) complexes. Theoret. Chim. Acta 94, 67–73 (1996). https://doi.org/10.1007/BF00194932
Received:
Accepted:
Issue Date:
DOI: https://doi.org/10.1007/BF00194932